Search Results (15)

γ-Alumina is often used as a support for hydrodesulfurization catalysts due to its excellent performance. During the catalytic reaction, the strong surface acidity of γ-alumina can induce a strong interaction between the active phase and the support. The reaction activity of the catalyst can be affected by changing the present mode of the active phase on the surface of the support. The (110) crystal plane, acting as the strongest acidity plane of γ-alumina, was selected for modification. The supports modified with boron and phosphorus were successfully constructed, and the acid strengths were quantified by simulating the adsorption of the relevant probe molecules: pyridine in correlation with surface electronic properties via density functional theory. The surface adsorption energy calculation shows that the boron-modified surface is able to moderately reduce the adsorption capacity of alumina, while that of the surface modified by phosphorus is found to be enhanced over the sites of a tetrahedral coordination structure; however, at the other unsaturated Al sites, this is obviously reduced. The results of introducing electric fields imply that applying horizontal electric fields changes the surface acidity of alumina under the premise of a stable structure. With the enhancement of the horizontal electric fields, the adsorption capacity of tetra-coordination sites on the original surface gradually decreases, while those of the others gradually increases. However, for the boron-modified surface, introducing horizontal electric fields can reduce the adsorption capacity of all sites. Hence, microwave-electric-field-assisted modification of B further reduces the surface acidity of alumina, making it beneficial for deep hydrodesulfurization reactions. Full article

Tetrahydrofurfuryl alcohol, a cost-effective biomass derivative, offers a sustainable path for synthesizing 1,5-pentanediol through hydrogenolysis. To develop the efficient production of 1,5-pentanediol from this alcohol, we have prepared a series of MgAl₂O₄-modified Pt/WO_x/γ-Al₂O₃ catalysts with varying compositions via impregnation–calcination methods. The physicochemical properties of these catalysts were subsequently characterized using diverse techniques. Characterization revealed that magnesia–alumina spinel modification enhanced Pt particle dispersion, CO adsorption on Pt/WO_x/γ-Al₂O₃, reduced Pt particle reduction temperature, diminished the acid content in the catalysts, and increased the surface oxygen vacancy concentration. These alterations appear to influence the catalyst performance, though other factors cannot be ruled out. Catalytic activity tests demonstrated that magnesia–alumina spinel modification improved tetrahydrofurfuryl alcohol hydrogenolysis activity and the 1,5-pentanediol selectivity of Pt/WO_x/γ-Al₂O₃. Optimal performance was achieved at 12% magnesia–alumina spinel loading, with a tetrahydrofurfuryl alcohol conversion of 47.3% and 1,5-pentanediol selectivity of 88.4%. Full article

A facile strategy for the design of porous supports was obtained by modifying the sol-gel method followed by the wet impregnation technique. In this respect, herein, the acidity of the γ-Al₂O₃ phase was modulated by adding basic MgO, La₂O₃ or ZnO promoters to form binary supported catalysts. The Ni and Co dispersion on the supports associated with their tunable acidity and morphologies resulted in highly porous supported alumina-based catalysts. The physicochemical properties of the solids were comprehensively investigated by XRD, textural properties, Raman and FTIR spectroscopy, SEM-EDS, TEM, EPR and XPS analyses. The catalytic performances in the esterification of glycerol in the presence of acetic acid (EG) for the acetins production were evaluated. The highly dispersed NiO and Co₃O₄ active species on binary porous supports produced synergistic effects appearing to be the reason for the activity of the solids in the EG reaction. Under the optimized reaction conditions, NiCo/MgO-Al₂O₃ was found to be a robust solid with superior catalytic performance and improved stability in four reaction cycles with 65.0% of glycerol conversion with an exclusive selectivity of 53% for triacetin. The presence of Co²⁺/Co³⁺ and Ni²⁺ strongly interacting with the spinel γ-Al₂O₃ and MgAl₂O₄ phases, the latter having a large number of lattice oxygen species, was considered another active component besides those of Ni and Co in the esterification of glycerol. Full article

In this work, we study the effect of modifying the metal loading (0.5–1.5 wt.% Pd and 0.1–1 wt.% Sn or In), the impregnation order of noble or promoter metal (Pd–Sn or Sn–Pd), and the type of promoter metal (Sn or In) during the preparation process for a Pd bimetallic catalyst, supported on γ-alumina, used in the catalytic reduction of nitrate. The deposition of the noble metal over the promoter metal, especially with Pd:Sn ratios (wt.) of 1:10 and 1:2, favored the hydrogen spillover rate and increased the H concentration on the catalyst surface, enhancing NH₄⁺ production. On the other hand, Pd–In catalysts showed higher activity than the Sn catalysts, as well as higher NH₄⁺ selectivity. The stability of the Pd–Sn/Al₂O₃ (1.5–1 wt.%) catalyst was evaluated in long-term experiments for the treatment of synthetic water (100 mg L⁻¹ NO₃⁻) and three different commercial drinking waters. This Pd–Sn/Al₂O₃ catalyst achieved a stable nitrate conversion for a duration of 50 h in the synthetic water treatment. However, the catalyst showed a significant activity loss in the presence of other ions (different to NO₃⁻) in the reaction medium, increasing slightly the selectivity to NH₄⁺. Full article

For the work presented herein nickel catalysts supported on γ-alumina extrudates (Ni/Al) with an egg-shell structure were prepared, using a modified Equilibrium Deposition Filtration (EDF) technique. Their performance was compared, for the biogas dry reforming reaction, with corresponding Ni/Al catalysts with a uniform structure, synthesized via the conventional wet impregnation method. The bulk and surface physicochemical characteristics of all final catalysts were determined using ICP-AES, N₂ adsorption-desorption isotherms, XRD, SEM, and TEM. A theoretical model describing the impregnation process for the EDF extrudates, based on the Lee and Aris model, was also developed. It was concluded that following specific impregnation conditions, the egg-shell macro-distributions can be successfully predicted, in agreement with the experimental results. It was shown that the Ni/Al catalysts with an egg-shell structure had a higher H₂ yield in comparison with the ones with a uniform structure. The difference in catalytic performance was attributed to the improved surface and structural properties of the egg-shell catalysts, resulting from the modified EDF technique used for their preparation. Full article

Elaboration of Pd-supported catalysts for catalytic combustion is, nowadays, considered as an imperative task to reduce the emissions of methane. This study provides new insight into the method of deposition, chemical state of Pd and oxygen storage capability of transition metal ions and their effects on the catalytic reactivity of supported catalysts for the combustion of methane. The catalyst with nominal composition La(Co_0.8Ni_0.1Fe_0.1)_0.85Pd_0.15O₃ was supported on SiO₂-modified/γ-alumina using two synthetic procedures: (i) aerosol assisted chemical vapor deposition (U-AACVD) and (ii) wet impregnation (Imp). A comparative analysis shows that a higher catalytic activity is established for supported catalyst obtained by wet impregnation, where the PdO-like phase is well dispersed and the transition metal ions display a high oxygen storage capability. The reaction pathway over both catalysts proceeds most probably through Mars–van Krevelen mechanism. The supported catalysts are thermally stable when they are aged at 505 °C for 120 h in air containing 1.2 vol.% water vapor. Furthermore, the experimentally obtained data on La(Co_0.8Ni_0.1Fe_0.1)_0.85Pd_0.15O₃—based catalyst, supported on monolithic substrate VDM^®Aluchrom Y Hf are simulated by using a two-dimensional heterogeneous model for monolithic reactor in order to predict the performance of an industrial catalytic reactor for abatement of methane emissions. Full article

Additive manufacturing (AM), for example, directed energy deposition (DED), may allow the processing of self-healing metal–matrix composites (SHMMCs). The sealing of cracks in these SHMMCs would be achieved via the melting of micro-encapsulated low melting point particulates (LMPPs), incorporated into the material during AM, by heat treatment of the part during service. Zn-Al alloys are good candidates to serve as LMPPs, for example, when the matrix of the MMC is made of an aluminum alloy. However, such powders should first be encapsulated by a thermal and diffusion barrier. Here, we propose a sol–gel process for encapsulation of a custom-made ZA-8 (Zn92Al8, wt.%) core powder in a ceramic alumina (Al₂O₃) shell. We first modify the surface of the ZA-8 powder with (12-phosphonododecyl)phosphonic acid (Di-PA) hydrophobic self-assembled monolayer (SAM) in order to prevent extensive hydrogen evolution and formation of non-uniform and porous oxide/hydroxide surface layers during the sol–gel process. Calcination for 1 h at 500 °C is found to be insufficient for complete boehmite-to-γ(Al₂O₃) phase transformation. Thermal stability tests in an air-atmosphere furnace at 600 °C for 1 h result in melting, distortion, and sintering into a brittle sponge (aggregate) of the as-atomized powder. In contrast, the core/shell powder is not sintered and preserves its spherical morphology, with no apparent “leaks” of the ZA-8 core alloy out of the ceramic encapsulation. Full article

The dry reforming of methane (DRM) process has attracted research interest because of its ability to mitigate the detrimental impacts of greenhouse gases such as methane (CH₄) and carbon dioxide (CO₂) and produce alcohols and clean fuel. In view of this importance of DRM, we disclosed the efficiency of a new nickel-based catalyst, which was promoted with magnesia (MgO) and supported over gamma-alumina (γ-Al₂O₃) doped with silica (SiO₂), toward DRM. The synthesized catalysts were characterized by H₂ temperature-programmed reduction (H₂-TPR), X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Thermogravimetric analysis (TGA), and Transmission electron microscopy (TEM) techniques. The effect of MgO weight percent loading (0.0, 1.0, 2.0, and 3.0 wt. %) was examined because the catalytic performance was found to be a function of this parameter. An optimum loading of 2.0 wt. % of MgO was obtained, where the conversion of CH₄ and CO₂ at 800 °C were 86% and 91%, respectively, while the syngas (H₂/CO) ratios relied on temperature and were in the range of 0.85 to 0.95. The TGA measurement of the best catalyst, which was operated over a 15-h reaction time, displayed negligible weight loss (<9.0 wt. %) due to carbon deposition, indicating the good resistance of our catalyst system to the deposition of carbon owing to the dopant and the modifier. TEM images showed the presence of multiwalled carbon nanotubes, confirming the TGA. Full article

Hydrogen is mainly produced by steam reforming of natural gas, a nonrenewable resource. Alternative and renewable routes for hydrogen production play an important role in reducing dependence on oil and minimizing the emission of greenhouse gases. In this work, butanol, a model compound of bio-oil, was employed for hydrogen production by steam reforming. The reaction was evaluated for 30 h in a tubular quartz reactor at 500 °C, atmospheric pressure, GHSV of 500,000 h⁻¹, and an aqueous solution feed of 10% v/v butanol. For this reaction, catalysts with 20 wt.% NiO were prepared by wet impregnation using three supports: γ-alumina and alumina modified with 10 wt.% of cerium and lanthanum oxides. Both promoters increased the reduction degree of the catalysts and decreased catalyst acidity, which is closely related to coke formation and deactivation. Ni/La₂O₃–Al₂O₃ presented a higher nickel dispersion (14.6%) which, combined with other properties, led to a higher stability, higher mean hydrogen yield (71%), and lower coke formation per mass (56%). On the other hand, the nonpromoted catalyst suffered a significant deactivation associated with coke formation favored by its highest acidity (3.1 µmol m⁻²). Full article

Gamma-alumina nanoparticles (γANPs) were obtained from a low-cost process by using natural bauxites. The γANPs materials were characterized by X-ray powder diffraction (XRPD), Fourier-transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller (BET) theory, scanning electron microscopy (SEM), atomic force microscopy (AFM), and were functionalized with N-cetyl-N, N, N, trimethylammonium bromide (CTAB), leading to CTAB modified γ-alumina nanoparticles (γANPs-CTAB). These novel functionalized γANPs-CTAB were characterized by XRPD, FTIR, and were used as an adsorbent for bisphenol-A (BPA) removal from water. Batch investigations were conducted under different experimental conditions (e.g., adsorbent dose, agitation time, initial concentration, and pH and surfactant loading) in order to optimize BPA adsorption and to identify the adsorption mechanisms in the system γANPs-CTAB-BPA. The effect of pH on the adsorption showed that the quantity of BPA removed increased remarkably until the pH value was 4, then remained almost constant until the pH value was up to 10, and then decreased for pH values greater than 10. For an initial BPA concentration of 20 mg/L and an adsorbent dose of 12.5 g/L at a pH value of 10, the removal efficiency achieved was 91.80 ± 0.21%. The adsorption mechanism was perfectly described by pseudo-second-order kinetics and the Langmuir isotherm. γANPs-CTAB materials were found to be effective adsorbents for BPA removal from water. Full article

γ-Al₂O₃ supported Ni-Pd catalysts with different Ni:Pd ratios were studied in the hydrogenation of two industrially-relevant platform molecules derived from biomass, namely levulinic acid and hydroxymethylfurfural. The bimetallic catalysts showed better performances in both processes in comparison to the monometallic counterparts, for which a too strong interaction with the alumina support reduced the activity. The behavior of the bimetallic catalysts was dependent on the Ni:Pd ratio, and interestingly also on the targeted hydrogenation reaction. The Pd-modified Ni-rich system behaves like pure Ni catalyst, but with a strongly boosted activity due to a higher number of Ni active sites available, Pd being considered as a spectator. This high activity was manifested in the levulinic acid hydrogenation with formic acid used as an internal hydrogen source. This behavior differs from the case of the Pd-rich system modified by Ni, which displayed a much higher Pd dispersion on the support compared to the monometallic Pd catalyst. The higher availability of the Pd active sites while maintaining a high surface acidity allows the catalyst to push the HMF hydrodeoxygenation reaction forward towards the green biopolymer precursor 2,5-bis(hydroxymethyl)-tetrahydrofuran, and in consequence to strongly modify the selectivity of the reaction. In that case, residual chlorine was proposed to play a significant role, while Ni was considered as a spectator. Full article

The objective of this work was to study the fast pyrolysis of a diglyceride intermediate compound during the conversion of triglycerides to fatty acids, esters and/or hydrocarbons. Dilaurin was selected as a model compound. Pyrolysis was conducted in a micro-pyrolyzer coupled to GC-MS equipment at 500, 550 and 600 °C for 15 s in the presence of sodium carbonate (Na₂CO₃) as the catalyst. Results were compared to pyrolysis data using γ-Al₂O₃ as a catalyst. At 600 °C with Na₂CO₃ almost total conversion of diglyceride was obtained, with the formation of 41.3% hydrocarbons (C3 to C13). In the same conditions using alumina as a catalyst 68.5% of hydrocarbons were obtained. Na₂CO₃ presented itself as an efficient feedstock modifier, allowing pre-cracking and partial deoxygenation of the load. The use of the Na₂CO₃ and γ-Al₂O₃ conjugated system in layers reduced the fatty acid content in the products, increasing both the reagent conversion and the hydrocarbon variety (C3 to C23). This work suggests that the use of a double bed catalytic reactor is suitable for performing a deoxygenating pretreatment and producing hydrocarbons compatible with current liquid fuels, being potentially useful for more complex raw materials such as those from biomass treatments. Full article

The increase of miniaturization and rise of powerhouses has caused a need for high-performing thermal interface materials (TIMs) that can transfer heat in electronic packaging. In this study, a thermoplastic polyurethane (PU)/alumina composite was produced via twin extrusion and was suggested as a TIM. The surfaces of the alumina particles were modified by γ-aminopropyltriethoxysilane (APTES) and then evaluated using Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) images revealed that the addition of surface-modified alumina was well adhered in the PU matrix. The tensile strength of the composite remained unchanged, while the Young’s modulus showed improvement as compared to the pure PU. The elongation at the break decreased as the filler loading increased, due to the brittle behavior of the composite. The viscoelastic elastic property analysis results revealed that there was an increase in the storage modulus of the composite and the glass transition temperature curve shifted to the right. The thermal conductivity of the composite showed that there was an 80.6% improvement in thermal conductivity with the incorporation of 40% APTES-treated alumina particles. Full article

An amino poly (styrene-co-maleic anhydride) polymer (ASMA) encapsulated γ-Al₂O₃ pellet material has been synthesized successfully. After loading with Pd species and modified with morpholine, the inorganic-organic hybrid material shows an excellent catalytic property in the selective hydrogenation of p-chloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN). In this procedure, morpholine can connect with the polymer layer in a form of amide bond and acts as an unparalleled immobilized dechlorination inhibitor, which can avoid further dechlorination efficiently and keeps stability due to the repulsive effect from the surviving C-O-C bond. The catalyst as prepared was characterized by using XRD, TGA, SEM, TEM, FT-IR, and ICP-OES, and it was further tested in the selective hydrogenation of p-CNB. It shows a supreme catalytic activity (almost 100%) and selectivity (up to 99.51%) after recycling for even 10 times, much superior to the blank alumina supported palladium (47.09%). Full article

The role of iron in two modes of integration into alumina catalysts was studied at 0.39 wt% Fe and tested in trichloroethylene combustion. One modified alumina was synthesized using the sol-gel method with Fe added in situ during hydrolysis; another modification was performed using calcined alumina, prepared using the sol-gel method and impregnated with Fe. Several characterization techniques were used to study the level of Fe modification in the γ-Al₂O₃ phase formed and to correlate the catalytic properties during trichloroethylene (TCE) combustion. The introduction of Fe in situ during the sol-gel process influenced the crystallite size, and three iron species were generated, namely, magnetite, maghemite and hematite. The impregnated Fe-alumina formed hematite and maghemite, which were highly dispersed on the γ-Al₂O₃ surface. The X-ray photoelectron spectra (XPS), FT-IR and Mössbauer spectroscopy analyses revealed how Fe interacted with the γ-Al₂O₃ lattice in both catalysts. The impregnated Fe-catalyst showed the best catalytic performance compared to the catalyst that was Fe-doped in situ by the sol-gel method; both had better catalytic activity than pure alumina. This difference in activity was correlated with the accessibility of the reactants to the hematite iron species on the surface. The chlorine poisoning for all three catalysts was less than 1.8%. Full article